CN108699349B

CN108699349B - Coloring composition, ink for inkjet recording, inkjet recording method, and ink cartridge for inkjet printer

Info

Publication number: CN108699349B
Application number: CN201780013211.0A
Authority: CN
Inventors: 立石桂一; 齐藤贵志; 坂井优介; 藤江贺彦; 永田美彰
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2016-02-24
Filing date: 2017-02-24
Publication date: 2021-03-12
Anticipated expiration: 2037-02-24
Also published as: WO2017146234A1; US10689535B2; EP3421548B1; JPWO2017146234A1; CN108699349A; EP3421548A4; US20180346743A1; EP3421548A1; JP6634507B2

Abstract

According to the present invention, there are provided a coloring composition comprising the compound represented by the general formula (1) described in the specification and at least one compound selected from the group consisting of the compound represented by the general formula (D) and the compound represented by the general formula (E), an ink for inkjet recording using the coloring composition, an ink jet recording method using the ink for inkjet recording, and an ink cartridge for inkjet printer filled with the ink for inkjet recording.

Description

Coloring composition, ink for inkjet recording, inkjet recording method, and ink cartridge for inkjet printer

Technical Field

The present invention relates to a coloring composition, an ink for inkjet recording, an inkjet recording method, and an ink cartridge for inkjet printer.

Background

As an ink jet recording method, a method of printing by causing ink droplets to fly and adhere to a recording medium such as paper is well known. This printing method enables high-resolution, high-quality images to be printed easily and at high speed with an inexpensive apparatus, and has been developed in recent years as an image forming method that can replace photographs, particularly in color printing.

For example,

patent documents

1 and 2 describe an ink for inkjet recording containing a xanthene compound.

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 2013-133396

Patent document 2: international publication No. 2015/105108

Disclosure of Invention

Technical problem to be solved by the invention

However, further improvement in performance is demanded for the field of dyes.

The present invention aims to provide a coloring composition which can form an image having excellent hue, chroma and tinting strength (print density), excellent light resistance, ozone resistance and moisture resistance, and excellent discharge stability in an ink jet printer, an ink for ink jet recording using the coloring composition, an ink jet recording method using the ink for ink jet recording, and an ink cartridge for ink jet printer filled with the ink for ink jet recording.

Means for solving the technical problem

The present inventors have conducted intensive studies and found that the above problems can be solved by the following means. In the present invention, by combining the compound represented by the general formula (1) and at least one compound selected from the group consisting of the compound represented by the general formula (D) and the compound represented by the general formula (E), it is possible to reduce (contribute to improvement in the discharge stability of the ink) the dye concentration contained in the coloring composition (ink) and to achieve both high coloring power (print density) and image fastness (light fastness, ozone fastness, and moisture fastness). The reasons for preference are as follows: by combining good hue and chroma and different pigment mother nuclei having high tinting strength, tinting strength and image fastness can be satisfied at a higher level than in the case of using each alone.

The detailed reason is not clear, but is estimated as follows: when the xanthene-based dye represented by the general formula (1) and at least one anthrapyridone dye selected from the group consisting of the compound represented by the general formula (D) and the compound represented by the general formula (E) are mixed (for example, in an ink for ink jet recording or an ink jet printed matter produced by an ink jet recording method: on an ink jet paper for exclusive use), the physical and chemical interactions are small, and the desired performance can be achieved without causing significant disadvantages such as reduction in light resistance and reduction in ejection stability of the ink.

< 1 > a coloring composition comprising:

a compound represented by the following general formula (1), and

at least one compound selected from the group consisting of the compound represented by the general formula (D) and the compound represented by the general formula (E).

[ chemical formula 1]

In the general formula (1), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group. R⁴、R⁹、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Each independently represents a hydrogen atom or a substituent. R²、R³、R⁷And R⁸Each independently represents a hydrogen atom, an alkyl group or a substituent represented by the following general formula (A), R²、R³、R⁷And R⁸At least 1 of them represents a substituent represented by the following general formula (A).

[ chemical formula 2]

In the general formula (a), X represents a substituent represented by the following general formula (X1), general formula (X2), or general formula (X3). Represents a bonding bond to a benzene ring.

[ chemical formula 3]

In the general formula (X1), R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵Each independently represents a hydrogen atom or a substituent. Wherein R is⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The following condition (i) or (ii) is satisfied. Denotes a bond to a sulfur atom.

Condition (i): r⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (ii): r⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵At least 2 of which represent carboxyl groups.

[ chemical formula 4]

In the general formula (X2), R⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷Each independently represents a hydrogen atom or a substituent. Wherein R is⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The following condition (iii) or (iv) is satisfied. Denotes a bond to a sulfur atom.

Condition (iii): r⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (iv): r⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷At least 2 of which represent carboxyl groups.

[ chemical formula 5]

In the general formula (X3), R⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷Each independently represents a hydrogen atom or a substituent. Wherein R is⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷The following condition (v) or (vi) is satisfied. Denotes a bond to a sulfur atom.

Condition (v): r⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (vi): r⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷At least 2 of which represent carboxyl groups.

General formula (D)

[ chemical formula 6]

In the general formula (D), R₂₁And R₂₂Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.

Y₂₁And Y₂₂Each independently represents a chlorine atom, a hydroxyl group, or a substituted or unsubstituted amino group, an alkoxy group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted naphthoxy group

Xd represents a 2-valent linking group.

M⁴Represents a hydrogen atom or a counter cation. M⁴Each may be the same or different.

[ chemical formula 7]

In the general formula (E), R₃₁Represents a hydrogen atom or a substituted or unsubstituted alkyl group.

Y₃₁Represents a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, or a morpholino group

M⁵Represents a hydrogen atom or a counter cation. M⁵Each may be the same or different.

X₃₁Represents a group represented by the following general formula (E-1).

[ chemical formula 8]

In the general formula (E-1), R₃₂、R₃₃、R₃₄、R₃₅And R₃₆Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or-COOM '(M' represents a hydrogen atom or a counter cation). Wherein R is₃₂、R₃₃、R₃₄、R₃₅And R₃₆At least 1 of them represents an alkyl group having 1 to 8 carbon atoms or-COOM'. Denotes a bond to a carbon atom.

< 2 > the colored composition according to < 1 >, wherein X in the general formula (A) represents a substituent represented by the general formula (X1), and R in the general formula (X1)⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The above condition (i) is satisfied.

< 3 > the colored composition according to < 1 >, wherein X in the general formula (A) represents a substituent represented by the general formula (X2), and R in the general formula (X2)⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The above condition (iii) is satisfied.

< 4 > the colored composition according to < 1 >, wherein X in the general formula (A) represents a substituent represented by the general formula (X3), and X in the general formula (X3)R⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷The above condition (v) is satisfied.

< 5 > the coloring composition according to any one of < 1 > to < 4 >, wherein,

the total content of the compound represented by the general formula (1), the compound represented by the general formula (D) and the compound represented by the general formula (E) is 2.0-5.0% by mass in the coloring composition.

< 6 > the coloring composition according to any one of < 1 > to < 5 >, wherein,

the mass ratio of W1/(WD + WE) is 90/10 to 60/40, where W1 represents the content of the compound represented by the general formula (1), WD represents the content of the compound represented by the general formula (D), and WE represents the content of the compound represented by the general formula (E).

< 7 > an ink for ink-jet recording, which uses the coloring composition of any one of < 1 > to < 6 >.

< 8 > an ink jet recording method using the ink for ink jet recording < 7 >.

< 9 > an ink cartridge for an ink jet printer filled with < 7 > said ink for ink jet recording.

Effects of the invention

According to the present invention, it is possible to provide a coloring composition which can form an image having excellent hue, chroma and coloring power (print density), and excellent light resistance, ozone resistance and moisture resistance, and which is excellent in discharge stability in an ink jet printer, an ink for ink jet recording using the coloring composition, an ink jet recording method using the ink for ink jet recording, and an ink jet printer cartridge filled with the ink for ink jet recording.

Drawings

FIG. 1 shows examples of compounds (1-11) in dimethylsulfoxide-d 6¹Graph of H-NMR (nuclear magnetic resonance) spectrum.

FIG. 2 shows dimethyl groups of exemplary compounds (1-18)In sulfoxide-d 6¹Graph of H-NMR spectrum.

FIG. 3 shows examples of compounds (1-26) in dimethylsulfoxide-d 6¹Graph of H-NMR spectrum.

FIG. 4 shows examples of compounds (1-30) in dimethylsulfoxide-d 6¹Graph of H-NMR spectrum.

Detailed Description

The present invention will be explained below.

First, a specific example of the substituent in the present invention is defined as substituent group a.

(substituent group A)

Examples thereof include a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an alkoxy group, an aryloxy group, a siloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imide group. These substituents may be further substituted, and examples of the further substituents include the substituents selected from substituent group a described above.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group include a linear, branched, and cyclic substituted or unsubstituted alkyl group, and a cycloalkyl group, a bicycloalkyl group, and a tricyclic structure having more ring structures. The alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in the substituents described below also represents an alkyl group of this concept.

The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl group, an eicosyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group and the like, the cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and examples thereof include a cyclohexyl group, a cyclopentyl group, a 4-n-dodecacyclohexyl group and the like, and the bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing 1 hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, and examples thereof include a bicyclo [1,2,2] heptan-2-yl group, a bicyclo [2, 2] octan-3-yl group and the like.

Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. Examples thereof include benzyl and 2-phenylethyl.

Examples of the alkenyl group include a linear, branched, cyclic, substituted or unsubstituted alkenyl group, including a cycloalkenyl group and a bicycloalkenyl group.

As the alkenyl group, preferred are a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms such as vinyl, allyl, isoprenyl, geranyl, oleyl and the like, and as the cycloalkenyl group, preferred are a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, i.e., a monovalent group obtained by removing 1 hydrogen atom from a cycloolefin having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like, as the bicycloalkenyl group, there may be mentioned a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, i.e., a monovalent group obtained by removing 1 hydrogen atom from a bicycloalkene having 1 double bond, such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl, and the like.

The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, a trimethylsilylethynyl group, or the like.

As the aryl group, preferred is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, an o-hexadecylaminophenyl group and the like.

The heterocyclic group is preferably a monovalent group obtained by removing 1 hydrogen atom from a 5-or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a 5-or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl or the like. Examples of the non-aromatic heterocyclic group include a morpholinyl group and the like.

The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a n-octyloxy group, a 2-methoxyethoxy group, or the like.

As the aryloxy group, preferred are substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, for example, phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecylaminophenoxy group and the like.

As the siloxy group, preferred is a substituted or unsubstituted siloxy group having 0 to 20 carbon atoms, such as trimethylsiloxy group, diphenylmethylsiloxy group and the like.

As the heterocyclic oxy group, preferred is a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group and the like.

As the acyloxy group, preferred are a formyloxy group, a substituted or unsubstituted alkylcarbonylacyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, an acetoxy group, a tert-valeryloxy group, a stearoyloxy group, a benzoyloxy group, a p-methoxyphenylcarbonyloxy group and the like.

As the carbamoyloxy group, preferred are substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-diethylcarbamoyloxy group, morpholinylcarbonyloxy group, N-di-N-octylaminocarbonyloxy group, N-N-octylcarbamoyloxy group and the like.

As the alkoxycarbonyloxy group, preferred are substituted or unsubstituted alkoxycarbonyloxy groups having 2 to 30 carbon atoms, such as methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group and the like.

As the aryloxycarbonyloxy group, preferred is a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a p-hexadecylphenoxycarbonyloxy group and the like.

The amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, and preferably includes an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and a triazinylamino group.

As the acylamino group, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, an acetylamino group, a tert-valerylamino group, a lauroylamino group, a benzoylamino group, a 3,4, 5-tri-n-octyloxyphenylcarbonylamino group and the like are preferably mentioned.

Preferred examples of the aminocarbonylamino group include a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonylamino group, a morpholinocarbonylamino group, and the like.

Preferred examples of the alkoxycarbonylamino group include substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, N-octadecyloxycarbonylamino group, and N-methyl-methoxycarbonylamino group.

As the aryloxycarbonylamino group, preferred are substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m-n-octyloxyphenoxycarbonylamino group and the like.

As the sulfamoylamino group, preferred is a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino group, N-dimethylaminosulfonylamino group, N-N-octylaminosulfonylamino group and the like.

As the alkyl group or arylsulfonylamino group, preferred are a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3, 5-trichlorophenylsulfonylamino group, p-tolylsulfonylamino group and the like.

The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, a methylthio group, an ethylthio group, a n-hexadecylthio group, or the like.

As the arylthio group, preferred is a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

As the heterocyclic thio group, preferred is a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

As the sulfamoyl group, preferred are substituted or unsubstituted sulfamoyl groups having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N' -phenylcarbamoyl) sulfamoyl group and the like.

The alkyl group or the arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-tolylsulfinyl group or the like.

Examples of the alkyl group or the arylsulfonyl group include a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group and a p-tolylsulfonyl group.

As the acyl group, preferred are a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group through a substituted or unsubstituted carbon atom having 2 to 30 carbon atoms, for example, an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a p-n-octyloxyphenylcarbonyl group, a 2-pyridylcarbonyl group, a 2-furanylcarbonyl group and the like.

The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, a p-tert-butylphenoxycarbonyl group, or the like.

The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, or a n-octadecyloxycarbonyl group.

Preferred examples of the carbamoyl group include a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-N-octylcarbamoyl group, an N- (methylsulfonyl) carbamoyl group and the like.

As the aryl group or the heterocyclic azo group, preferred are a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, a phenylazo group, a p-chlorophenylazo group, a 5-ethylthio-1, 3, 4-thiadiazol-2-ylazo group and the like.

Preferable examples of the imide group include an N-succinimidyl group, an N-phthalimidyl group and the like.

The phosphine group is preferably a substituted or unsubstituted phosphine group having 0 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino, or the like.

The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl, or the like.

As the phosphinyl group, preferred is a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, for example, a diphenoxyphosphinyl group, a dioctyloxyphosphinyl group and the like.

As the phosphinyl amino group, preferred is a substituted or unsubstituted phosphinyl amino group having 0 to 30 carbon atoms, for example, dimethoxyphosphinyl amino group, dimethylaminonephosphinyl amino group.

The silyl group is preferably a substituted or unsubstituted silyl group having 0 to 30 carbon atoms, for example, a trimethylsilyl group, a tert-butyldimethylsilyl group, a phenyldimethylsilyl group, or the like.

Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, a quaternary ammonium group, a hydroxyl group substituted with an s-triazine ring, and the like. Particularly preferred are sulfo groups and hydroxyl groups having carboxyl groups substituted with s-triazine rings, and among these, sulfo groups and carboxyl groups are particularly preferred. The ionic hydrophilic group may contain a cation or an anion, and a state containing a cation or an anion is referred to as a salt state. The carboxyl group, phosphono group, sulfo group and hydroxyl group may be in the form of a salt, and examples of the counter cation forming the salt include an ammonium ion, an alkali metal ion (e.g., lithium ion, sodium ion, potassium ion) and an organic cation (e.g., tetramethylammonium ion, tetramethylguanidine ion, tetramethylphosphonium ion), and are preferably a lithium salt, a sodium salt, a potassium salt or an ammonium salt, more preferably a sodium salt or a mixed salt containing a sodium salt as a main component, and most preferably a sodium salt.

In the present invention, when the compound is a salt, the salt is dissociated in an ion and exists in the water-soluble ink.

[ Compound represented by the general formula (1) ]

A compound represented by the following general formula (1) will be described.

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

In the general formula (1), R¹¹、R¹³、R¹⁴、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Each independently represents a hydrogen atom or a substituent. When R is¹¹、R¹³、R¹⁴、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰When a substituent is represented, examples of the substituent include a substituent selected from the above substituent group a.

Preferably R¹¹、R¹³、R¹⁴、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Represents a hydrogen atom.

In the general formula (1), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group, and from the viewpoint of availability of raw materials and ease of synthesis, the alkyl group preferably has 1 to 6 carbon atoms, more preferably has 1 to 3 carbon atoms, and still more preferably is a methyl group or an ethyl group. And, R¹、R⁵、R⁶And R¹⁰The alkyl group may have a substituent, and examples of the substituent include substituents selected from the substituent group a.

In the general formula (1), R⁴、R⁹、R¹²And R¹⁵Each independently represents a hydrogen atom or a substituent. As R⁴、R⁹、R¹²And R¹⁵The substituent in the case of representing a substituent is preferably an alkyl group or an ionic hydrophilic group.

The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The ionic hydrophilic group is preferably a carboxyl group, a sulfo group or a phosphono group. Examples of the counter cation of the ionic hydrophilic group include a hydrogen atom (proton), an alkali metal cation (lithium ion, sodium ion, or potassium ion), an ammonium ion, and the like, but from the viewpoint of ease of synthesis (ease of handling as a dye powder), an alkali metal cation is preferable.

Preferably R⁴、R⁹、R¹²And R¹⁵At least 1 of them represents an ionic hydrophilic group, more preferably 2 or more representAn ionic hydrophilic group.

Preferably R¹²And R¹⁵Represents an ionic hydrophilic group, and R⁴And R⁹Represents a hydrogen atom, or R⁴And R⁹Represents an ionic hydrophilic group, and R¹²And R¹⁵Represents a hydrogen atom, more preferably R¹²And R¹⁵Represents an ionic hydrophilic group, and R⁴And R⁹Represents a hydrogen atom.

Preferably R⁴And R⁹Each independently represents a hydrogen atom, a sulfo group or a carboxyl group, more preferably a hydrogen atom or a sulfo group.

Preferably R¹²And R¹⁵Each independently represents a hydrogen atom, a sulfo group or a carboxyl group, more preferably a hydrogen atom or a sulfo group.

In the general formula (1), R²、R³、R⁷And R⁸Each independently represents a hydrogen atom, an alkyl group or a substituent represented by the general formula (A), R²、R³、R⁷And R⁸At least 1 of them represents a substituent represented by the above general formula (A).

When R is²、R³、R⁷And R⁸When the alkyl group is represented, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group or an ethyl group. And, R²、R³、R⁷And R⁸The alkyl group may have a substituent, and examples of the substituent include substituents selected from the substituent group a.

Preferably R²And R⁷Each independently represents a substituent represented by the general formula (A), and R³And R⁸Represents alkyl, or R³And R⁸Each independently represents a substituent represented by the general formula (A), and R²And R⁷Represents an alkyl group, more preferably R²And R⁷Each independently represents a substituent represented by the general formula (A), and R³And R⁸Represents an alkyl group.

In the general formula (a), X represents a substituent represented by the general formula (X1), the general formula (X2), or the general formula (X3).

Examples of the counter cation of the carboxyl group in the general formula (X1), the general formula (X2), or the general formula (X3) include a hydrogen atom (proton), an alkali metal cation (lithium ion, sodium ion, or potassium ion), an ammonium ion, and the like, but the alkali metal cation is preferable.

In the general formula (X1), R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵Each independently represents a hydrogen atom or a substituent. Wherein R is⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The following condition (i) or (ii) is satisfied.

In the general formula (X1), R is preferably⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The above condition (i) is satisfied. That is, R is preferred⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The number of the medium hydroxyl groups is preferably 1 to 3, more preferably 1 to 2, and further preferably 1. The number of carboxyl groups is more preferably 1 to 3, and still more preferably 1 to 2.

Preferably R⁴⁰³Represents a hydroxyl group, and R⁴⁰²Represents a carboxyl group, or R⁴⁰¹Represents a hydroxyl group, and R⁴⁰²Represents a carboxyl group, more preferably R⁴⁰¹Represents a hydroxyl group, and R⁴⁰²Represents a carboxyl group.

As R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The substituent when representing a substituent includes a substituent selected from the substituent group A, preferably an alkyl group or an alkoxy group, more preferably a group having 1 to 6 carbon atomsThe alkyl group or alkoxy group is more preferably an alkyl group or alkoxy group having 1 to 3 carbon atoms, and particularly preferably a methyl group or methoxy group. And as R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The substituent in the case of representing a substituent includes a carboxyl group, a chlorine atom, a nitro group, or a trifluoromethyl group, more preferably a carboxyl group, a chlorine atom, or a nitro group, and still more preferably a carboxyl group. In particular, when R⁴⁰¹Represents a hydroxyl group, and R⁴⁰²When representing a carboxyl group, R is preferably⁴⁰⁴The above substituent (carboxyl group, chlorine atom, nitro group or trifluoromethyl group).

In the general formula (X1), when R is⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵When the above condition (ii) is satisfied, R is preferably⁴⁰²And R⁴⁰⁴Represents a carboxyl group.

Specific examples of the group represented by the general formula (X1) are shown below, but the group is not limited to these. In the structural formula of the specific compound described below, Me represents a methyl group. Denotes a bond to a sulfur atom.

[ chemical formula 14]

[ chemical formula 15]

In the general formula (X2), R⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷Each independently represents a hydrogen atom or a substituent. Wherein R is⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The following condition (iii) or (iv) is satisfied.

In the general formula (X2), R is preferred⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The condition (iii) is satisfied. That is, R is preferred⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

As R⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The substituent in the case of representing a substituent is a substituent selected from the above substituent group A, and is preferably an alkyl group or an alkoxy group, more preferably an alkyl group or an alkoxy group having 1 to 6 carbon atoms, still more preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a methyl group or a methoxy group.

R⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The number of the medium hydroxyl groups is preferably 1 to 3, more preferably 1 to 2, and further preferably 1. The number of carboxyl groups is more preferably 1 to 2, and still more preferably 1.

Preferably R⁵⁰⁴Represents a hydroxyl group, and R⁵⁰³Represents a carboxyl group, or R⁵⁰⁴Represents a hydroxyl group, and R⁵⁰⁵Represents a carboxyl group, more preferably R⁵⁰⁴Represents a hydroxyl group, and R⁵⁰³Represents a carboxyl group.

Specific examples of the group represented by the general formula (X2) are shown below, but the present invention is not limited to these. Denotes a bond to a sulfur atom.

[ chemical formula 16]

[ chemical formula 17]

In the general formula (X3), R is preferred⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷The condition (v) is satisfied. That is, R is preferred⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

As R⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷The substituent in the case of representing a substituent is a substituent selected from the above substituent group A, and is preferably an alkyl group or an alkoxy group, more preferably an alkyl group or an alkoxy group having 1 to 6 carbon atoms, still more preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a methyl group or a methoxy group.

R⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷The number of the medium hydroxyl groups is preferably 1 to 3, more preferably 1 to 2, and further preferably 1. The number of carboxyl groups is more preferably 1 to 2, and still more preferably 1.

Preferably R⁶⁰⁶Represents a hydroxyl group, and R⁶⁰⁵Represents a carboxyl group, or R⁶⁰³Represents a hydroxyl group, and R⁶⁰²Represents a carboxyl group, more preferably R⁶⁰⁶Represents a hydroxyl group, and R⁶⁰⁵Represents a carboxyl group.

Specific examples of the group represented by the general formula (X3) are shown below, but the group is not limited to these. Denotes a bond to a sulfur atom.

[ chemical formula 18]

[ chemical formula 19]

The compound represented by the above general formula (1) is preferably a compound represented by the following general formula (2), general formula (3) or general formula (4).

[ chemical formula 20]

In the general formula (2), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group. R⁴、R⁹、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Each independently represents a hydrogen atom or a substituent. R³And R⁸Each independently represents a hydrogen atom or an alkyl group. R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵Each independently represents a hydrogen atom or a substituent. It is composed ofIn, R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵Satisfies the following condition (i-1) or (ii-1). R⁴⁰⁶、R⁴⁰⁷、R⁴⁰⁸、R⁴⁰⁹And R⁴¹⁰Each independently represents a hydrogen atom or a substituent. Wherein R is⁴⁰⁶、R⁴⁰⁷、R⁴⁰⁸、R⁴⁰⁹And R⁴¹⁰Satisfies the following condition (i-2) or (ii-2).

Condition (i-1): r⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (ii-1): r⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵At least 2 of which represent carboxyl groups.

Condition (i-2): r⁴⁰⁶、R⁴⁰⁷、R⁴⁰⁸、R⁴⁰⁹And R⁴¹⁰At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (ii-2): r⁴⁰⁶、R⁴⁰⁷、R⁴⁰⁸、R⁴⁰⁹And R⁴¹⁰At least 2 of which represent carboxyl groups.

[ chemical formula 21]

In the general formula (3), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group. R⁴、R⁹、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Each independently represents a hydrogen atom or a substituent. R³And R⁸Each independently represents a hydrogen atom or an alkyl group. R⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷Each independently represents a hydrogen atom or a substituent. Wherein R is⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷Represents the following condition (iii-1) or (iv-1). R⁵⁰⁸、R⁵⁰⁹、R⁵¹⁰、R⁵¹¹、R⁵¹²、R⁵¹³And R⁵¹⁴Each independently represents a hydrogen atom or a substituent. Wherein R is⁵⁰⁸、R⁵⁰⁹、R⁵¹⁰、R⁵¹¹、R⁵¹²、R⁵¹³And R⁵¹⁴The following condition (iii-2) or (iv-2) is satisfied.

Condition (iii-1): r⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (iv-1): r⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷At least 2 of which represent carboxyl groups.

Condition (iii-2): r⁵⁰⁸、R⁵⁰⁹、R⁵¹⁰、R⁵¹¹、R⁵¹²、R⁵¹³And R⁵¹⁴At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (iv-2): r⁵⁰⁸、R⁵⁰⁹、R⁵¹⁰、R⁵¹¹、R⁵¹²、R⁵¹³And R⁵¹⁴At least 2 of which represent carboxyl groups.

[ chemical formula 22]

In the general formula (4), R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group. R⁴、R⁹、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Each independently represents a hydrogen atom or a substituent. R³And R⁸Each independently represents a hydrogen atom or an alkyl group. R⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷Each independently represents a hydrogen atom or a substituent. Wherein R is⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷Satisfies the following condition (v-1) or (vi-1). R⁶⁰⁸、R⁶⁰⁹、R⁶¹⁰、R⁶¹¹、R⁶¹²、R⁶¹³And R⁶¹⁴Each independently represents a hydrogen atom or a substituent. Wherein R is⁶⁰⁸、R⁶⁰⁹、R⁶¹⁰、R⁶¹¹、R⁶¹²、R⁶¹³And R⁶¹⁴Satisfies the following condition (v-2) or (vi-2).

Condition (v-1): r⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (vi-1): r⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷At least 2 of which represent carboxyl groups.

Condition (v-2): r⁶⁰⁸、R⁶⁰⁹、R⁶¹⁰、R⁶¹¹、R⁶¹²、R⁶¹³And R⁶¹⁴At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group.

Condition (vi-2): r⁶⁰⁸、R⁶⁰⁹、R⁶¹⁰、R⁶¹¹、R⁶¹²、R⁶¹³And R⁶¹⁴At least 2 of which represent carboxyl groups.

R in the general formula (2)¹、R⁴、R⁵、R⁶、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Are each as defined for R in the general formula (1)¹、R⁴、R⁵、R⁶、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Similarly, the preferred ranges are also the same.

R in the general formula (2)³And R⁸Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group or an ethyl group. The alkyl group may have a substituent, and examples of the substituent include substituents selected from the substituent group a.

R in the general formula (2)⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The above condition (i-1) is preferably satisfied. That is, R is preferred⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group. R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵With R in each formula (X1)⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The same is true.

R in the general formula (2)⁴⁰⁶、R⁴⁰⁷、R⁴⁰⁸、R⁴⁰⁹And R⁴¹⁰The above condition (i-2) is preferably satisfied. That is, R is preferred⁴⁰⁶、R⁴⁰⁷、R⁴⁰⁸、R⁴⁰⁹And R⁴¹⁰At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group. R⁴⁰⁶、R⁴⁰⁷、R⁴⁰⁸、R⁴⁰⁹And R⁴¹⁰With R in each general formula (2)⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The same is true.

R in the general formula (3)¹、R⁴、R⁵、R⁶、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Are each as defined for R in the general formula (1)¹、R⁴、R⁵、R⁶、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Similarly, the preferred ranges are also the same.

R in the general formula (3)³And R⁸Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group or an ethyl group. The alkyl group may have a substituent, and examples of the substituent include substituents selected from the substituent group a.

R in the general formula (3)⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷It is preferable that the above condition (iii-1) is satisfied. That is, R is preferred⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group. R⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷With R in each formula (X2)⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The same is true.

R in the general formula (3)⁵⁰⁸、R⁵⁰⁹、R⁵¹⁰、R⁵¹¹、R⁵¹²、R⁵¹³And R⁵¹⁴It is preferable that the above condition (iii-2) is satisfied. That is, R is preferred⁵⁰⁸、R⁵⁰⁹、R⁵¹⁰、R⁵¹¹、R⁵¹²、R⁵¹³And R⁵¹⁴At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group. R⁵⁰⁸、R⁵⁰⁹、R⁵¹⁰、R⁵¹¹、R⁵¹²、R⁵¹³And R⁵¹⁴With R in each formula (3)⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The same is true.

R in the general formula (4)¹、R⁴、R⁵、R⁶、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Are each as defined for R in the general formula (1)¹、R⁴、R⁵、R⁶、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Similarly, the preferred ranges are also the same.

R in the general formula (4)³And R⁸Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group or an ethyl group. The alkyl group may have a substituent, and examples of the substituent include substituents selected from the substituent group a.

R in the general formula (4)⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷It is preferable that the above condition (v-1) is satisfied. That is, R is preferred⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group. R⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷With R in each formula (X3)⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷The same is true.

R in the general formula (4)⁶⁰⁸、R⁶⁰⁹、R⁶¹⁰、R⁶¹¹、R⁶¹²、R⁶¹³And R⁶¹⁴It is preferable that the above condition (v-2) is satisfied. That is, R is preferred⁶⁰⁸、R⁶⁰⁹、R⁶¹⁰、R⁶¹¹、R⁶¹²、R⁶¹³And R⁶¹⁴At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group. R⁶⁰⁸、R⁶⁰⁹、R⁶¹⁰、R⁶¹¹、R⁶¹²、R⁶¹³And R⁶¹⁴With R in each general formula (4)⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷The same is true.

Specific examples of the compound represented by the general formula (1) are given below, but the compound is not limited thereto. In the structural formulae of the following specific compounds, Me represents a methyl group and Et represents an ethyl group.

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

[ chemical formula 28]

In addition, specific synthesis methods of the compounds represented by the general formula (1) are illustrated by examples.

[ Compound represented by the general formula (D) ]

[ chemical formula 29]

Y₂₁And Y₂₂Each independently represents a chlorine atom, a hydroxyl group, or a substituted or unsubstituted amino group, an alkoxy group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted naphthoxy group.

Xd represents a 2-valent linking group.

When R is₂₁And R₂₂When the alkyl group represents an alkyl group, the alkyl group may be any of a linear, branched or cyclic (cycloalkyl group), and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group is a cyclic alkyl group, a cycloalkyl group is preferable.

The alkyl group is more preferably a linear or branched alkyl group.

Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a n-hexyl group, a n-octyl group, a cycloalkyl group and the like.

When R is₂₁And R₂₂When an alkyl group is represented, the alkyl group may have a substituent. As the substituent, a hydroxyl group, a cyano group, or an alkyl group-substituted amino group is preferable.

When substituted by hydroxy or cyano, ethyl is most preferred as alkyl.

Examples of the alkyl-substituted amino group include a monoalkylamino group and a dialkylamino group, and the alkyl group is preferably a straight chain or a branched chain. Preferably a C1-8 alkyl-substituted monoalkylamino group or dialkylamino group, more preferably a C1-6 alkyl-substituted monoalkylamino group or dialkylamino group, still more preferably a C1-4 alkyl-substituted monoalkylamino group or dialkylamino group, and particularly preferably a methyl-or ethyl-substituted monoalkylamino group or dialkylamino group.

From the viewpoint of availability of raw materials, R₂₁And R₂₂A hydrogen atom or an unsubstituted alkyl group is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is further preferable.

In the general formula (D), Y₂₁And Y₂₂Each independently represents a chlorine atom, a hydroxyl group, or a substituted or unsubstituted amino group, an alkoxy group, a substituted or unsubstituted phenoxy group, or a substituted or unsubstituted naphthoxy group.

When Y is₂₁And Y₂₂When an amino group is represented, the amino group may have a substituent. As the substituent, an alkyl group or an aryl group is preferable.

When Y is₂₁And Y₂₂When an amino group (alkylamino group) having a substituent as an alkyl group is represented, the amino group may be a monoalkylamino group or a dialkylamino group.

The alkyl group may be any of linear, branched or cyclic (cycloalkyl).

When the alkyl group is a straight-chain or branched alkyl group, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a butyl group, and a 2-ethylhexyl group.

When the alkyl group is a linear or branched alkyl group, the alkyl group may have a substituent, and the further substituent is preferably an alkylamino group, an aryl group, a sulfo group, a carboxyl group, or a hydroxyl group. When the alkyl group further has a substituent, the alkyl group is preferably an alkyl group having a substituent selected from the group consisting of a sulfo group, a carboxyl group and a hydroxyl group, or an alkyl group having an aryl group (aralkyl group), or an alkyl group having an alkylamino group.

The alkyl group having a substituent selected from the group consisting of a sulfo group, a carboxyl group and a hydroxyl group is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group and the like.

Specific examples of the monoalkylamino group or dialkylamino group having a sulfo group or a carboxyl group include a 2-sulfoethylamino group, a carboxymethylamino group, a 2-carboxyethylamino group, a 1, 2-dicarboxyethylamino group, a di (carboxymethyl) amino group, and the like.

Specific examples of the monoalkylamino group or dialkylamino group having a hydroxyl group include a hydroxyethylamino group, a dihydroxyethylamino group and the like.

The amino group having an aralkyl group is preferably an amino group having a phenyl-substituted alkyl group having 1 to 6 carbon atoms, and examples thereof include a benzylamino group, a phenethylamino group, and a phenylpropylamino group.

The alkylamino group as the above-mentioned further substituent may be a monoalkylamino group or a dialkylamino group, and specific examples and preferable ranges of the above-mentioned alkylamino group and the above-mentioned Y₂₁And Y₂₂The alkylamino groups of (a) are the same.

When Y is₂₁And Y₂₂When an amino group having a cycloalkyl group is represented, the cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms, and examples thereof include a cyclohexyl group and a cyclopentyl group.

When Y is₂₁And Y₂₂When an amino group having an aryl group as a substituent (arylamino group) is represented, a phenyl group or naphthyl group-substituted amino group is preferable.

As the phenyl-substituted amino group, an anilino group is preferred. In the anilino group, at least one substituent selected from the group consisting of a sulfo group and a carboxyl group may be further substituted in addition to an unsubstituted anilino group on the benzene ring, and examples thereof include a 2, 5-disulfoanilino group, a 3-sulfoanilino group, a 2-sulfoanilino group, a 4-sulfoanilino group, a 2-carboxy-4-sulfoanilino group, and a 2-carboxy-5-sulfoanilino group.

In the naphthyl-substituted amino group (naphthylamino group), the naphthyl group may be further substituted with a sulfo group in addition to the unsubstituted naphthylamino group, and examples thereof include a 3,6, 8-trisulfo-1-naphthylamino group, a4, 6, 8-trisulfo-2-naphthylamino group, a 3,6, 8-trisulfo-2-naphthylamino group, a4, 8-disulfo-2-naphthylamino group and the like.

When Y is₂₁And Y₂₂When the alkoxy group is represented, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or a butoxy group.

When Y is₂₁And Y₂₂When the phenoxy group represents a phenoxy group, the phenoxy group may be an unsubstituted phenoxy group or a substituted phenoxy group. The substituent is preferably at least one substituent selected from the group consisting of a sulfo group, a carboxyl group, an acetamido group, an amino group, and a hydroxyl group. Examples of the phenoxy group substituted with a substituent selected from the group consisting of a sulfo group, a carboxyl group, an acetamido group, an amino group and a hydroxyl group include a 4-sulfophenoxy group, a 4-carboxyphenoxy group, a 4-acetamido-phenoxy group, a 4-aminophenoxy group, a 4-hydroxyphenoxy group, a 3, 5-dicarboxyphenoxy group and the like.

When Y is₂₁And Y₂₂When a naphthyloxy group is mentioned, the naphthyloxy group may be an unsubstituted naphthyloxy group or a substituted naphthyloxy group. The substituent is preferably at least one substituent selected from the group consisting of a sulfo group, a carboxyl group, an acylamino group, an amino group and a hydroxyl group. Examples of the naphthyloxy group substituted with a substituent selected from the group consisting of a sulfo group, a carboxyl group, an acylamino group, an amino group and a hydroxyl group include a 6-carboxy-2-naphthyloxy group and the like.

From the viewpoint of moisture resistance, Y₂₁And Y₂₂Preferred is a chlorine atom, a hydroxyl group, an unsubstituted amino group, a substituted or unsubstituted phenoxy group or a substituted or unsubstituted naphthoxy group, and particularly preferred is a substituted phenoxy group or a substituted naphthoxy group, and among them, a phenoxy group having a carboxyl group or a naphthoxy group having a carboxyl group is most preferred.

In the general formula (D), Xd represents a 2-valent linking group. Examples of the 2-valent linking group include 2-valent groups having nitrogen atoms or oxygen atoms at both ends of a hydrocarbon residue having 1 to 20 carbon atoms and containing a nitrogen atom, an oxygen atom, or a sulfur atom, and having a bond of the nitrogen atom or the oxygen atom at both ends, and specifically include:

-N(H)_m(-A-)_nN(H)_m-or

-O-A-O-

(wherein A is a 2-valent hydrocarbon residue having 1 to 20 carbon atoms and may contain a nitrogen atom, an oxygen atom or a sulfur atom, n represents 1 or 2, m represents 1 or 0, m represents 1 when n is 1, and m represents 0 when n is 2).

Examples of the hydrocarbon residue having 1 to 20 carbon atoms in the valence 2 of A include a 2-valent aliphatic group having 1 to 15 carbon atoms and containing 1 to 2 hetero atoms (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.), an aromatic group having 3 to 10 carbon atoms in the valence 2 and preferably having 5 to 10 carbon atoms and containing 1 to 3 hetero atoms (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.), and a 2-valent group in which the aliphatic group is bonded to the aromatic group. These groups may have a substituent (e.g., a sulfo group, a carboxyl group, an amino group, or an alkyl group having 1 to 10 carbon atoms in the case of an aromatic group).

Examples of the aliphatic group include (poly) methylene groups having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms such as methylene, dimethylene (ethylene), trimethylene (propylene), 2-methyltrimethylene (2-methylpropylene), tetramethylene (butylene), hexamethylene and the like, (poly) methylene groups having 1 to 6 carbon atoms, cycloalkylene groups having 5 to 7 carbon atoms such as cyclopentane-1, 2-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 2-diyl, cyclohexane-1, 3-diyl, cyclohexane-1, 4-diyl and cycloheptane-diyl, methylenecyclohexane-1, 4-diylmethylene (-CH)₂-C₆H₁₀-CH₂-), methylenebicyclohexane-diyl (-C)₆H₁₀-CH₂-C₆H₁₀-), methylenebis (methylcyclohexane-diyl) { -C₆H₁₀(CH₃)-CH₂-C₆H₁₀(CH₃) - }, cyclohexane-diyl-dimethylene (-CH)₂-C₆H₁₀-CH₂-) or the like, and an aliphatic ring having 1 to 10 carbon atoms and 5 to 7 carbon atoms, which may be substituted with an alkyl group having 1 to 10 carbon atomsGroup, methyleneoxymethylene (-CH)₂-O-CH₂-) bis (dimethylene) amino (-C)₂H₄-NH-C₂H₄-) methylene thiomethylene (-CH)₂-S-CH₂-) oxy bicyclohexane-diyl (-C)₆H₁₀-O-C₆H₁₀-) and the like, and aliphatic groups having 1 to 7 carbon atoms containing hetero atoms.

As the aromatic group having a valence of 2, a phenylene group (-C)₆H₄-) naphthylene (-C)₁₀H₆-) and the like, and an aromatic group having 6 to 10 carbon atoms.

The 2-valent group formed by bonding the aliphatic group and the aromatic group includes xylylene (-CH)₂-C₆H₄-CH₂-) and the like.

More preferable examples of the group A include a dimethylene group, a hexamethylene group, a 1, 3-xylylene group, a methylenebicyclohexane-4, 1-diyl group, a methylenebis (2-methylcyclohexane-4, 1-diyl) group, and a cyclohexane-1, 3-diyl-dimethylene group.

Examples of the 2-valent linking group Xd include 1, 2-diaminoethylene (-NH-CH)₂CH₂-NH-), 1, 4-diaminobutylidene (-NH-C)₄H₈-NH-), 1, 6-diaminohexylidene (-NH-C)₆H₁₂Diaminoalkylene such as-NH-), 1, 4-piperazinediyl (-NC)₄H₈N-, 1, 4-diaminophenylene (-NH-C)₆H₄-p-NH-), 1, 3-diaminophenylene (-NH-C)₆H₄Diaminophenylene such as-m-NH-), 4-sulfo-1, 3-diaminophenylene { -NH-C₆H₄(p-SO₃H) Substituted diaminophenylene such as-m-NH-, 5-carboxy-1, 3-diaminophenylene and 1, 3-diaminoxylylene (-NH-CH)₂-C₆H₄-m-CH₂-NH-), 1, 4-diaminobenzenedimethyl (-NH-CH)₂-C₆H₄-p-CH₂-NH-), 4' -diamino-2-sulfo-diphenylamino { -NH-C₆H₄(m-SO₃H)-NH-C₆H₄-p-NH- }, 4' -diaminodicyclohexyl-methyl (-NH-C)₆H₁₀-4-CH₂-C₆H₁₀-4 ' -NH-), 4 ' -diamino-3, 3 ' -dimethyldicyclohexyl-methyl-alkyl { -NH-C₆H₁₀(3-CH₃)-4-CH₂-C₆H₁₀(3’-CH₃) -4' NH- }, 1, 3-bis (aminomethyl) cyclohexyl (-NH-CH)₂-C₆H₁₀-3-CH₂-NH-), dioxyethylene (-O-CH)₂CH₂-O-), 1, 4-dioxybutylidene (-O-C)₄H₈-O-), 2' -dioxyethyl ether group (-O-CH)₂CH₂-O-CH₂CH₂Dioxy-substituted alkylene such as-O-), 1, 4-dioxyphenylene (-O-C)₆H₄-p-O-), 1, 3-dioxyphenylene (-O-C)₆H₄-m-O-), 4' -dioxydiphenyl ether (-O-C)₆H₄-p-O-C₆H₄-p-O-), 4' -dioxyphenylenesulfide (-O-C)₆H₄-p-S-C₆H₄-p-O-), 2, 5-norbornanediamino and 2, 6-norbornanediamino, 1, 4-dioxymethylcyclohexylene (-O-CH)₂-C₆H₁₀-4-CH₂-O-), and the like.

In addition, in the formula-N (H)_m(-A-)_nN(H)_mIn (E), examples of the group in which n is 2 and m is 0 include the above-mentioned 1, 4-piperazinediyl (-NC)₄H₈N-), etc.

Xd is preferably diaminoethylene, 1, 4-piperazinediyl, 1, 3-diaminobenzenedimethyl, 4 ' -diaminodicyclohexylmethane, 4 ' -diamino-3, 3 ' -dimethyldicyclohexylmethane, 1, 3-bis (aminomethyl) cyclohexane.

In the general formula (D), M⁴Represents a hydrogen atom or a counter cation. M⁴Each may be the same or different.

In the above general formula (D), when M is⁴In the form of a free acid when it is a hydrogen atom, when M is⁴In the form of a salt in the case of a counter cation.

Examples of the counter cation for forming the salt include a counter cation having a valence of 1, and preferably include an alkali metal ion, an ammonium ion, an organic cation, and the like.

Examples of the organic cation include cations obtained by adding a hydrogen ion to an alkylamine or an alkanolamine, examples of the alkylamine include trimethylamine and triethylamine, and examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.

From the viewpoint of solubility, alkali metal ions are preferred, and lithium ions, sodium ions, and potassium ions are more preferred. Sodium ions are particularly preferable from the viewpoint of inexpensive production.

In the general formula (D), M⁴Each may be the same or different. That is, the form in which the compound represented by the general formula (D) is a salt includes a case in which all of the sulfo groups are in the form of a salt and a case in which a part of the sulfo groups are in the form of a free acid and a part of the sulfo groups are in the form of a salt. The counter cation forming the salt may be one kind or plural kinds.

The groups (for example, carboxyl group) which can be in the form of a salt with a group other than a sulfo group are the same as described above.

Specific examples of the anthrapyridone compound represented by the general formula (D) are shown in the following tables. In the table, "diaminoethylene" means 1, 2-diaminoethylene (-NH-CH)₂CH₂-NH-). And "Ph" represents a phenyl group, for example, "PhO" represents a phenoxy group, and "NHPh" represents an anilino group, and the others are the same. And "NHPh (p-SO)₃H) "represents 4-sulfoanilino group (" p-SO3H "represents that the sulfonic acid group is located at the para-position of the phenyl group)," NHPh (COOH)2(3,5) "represents 3, 5-dicarboxylanilino {" Ph (COOH)2(3,5) "represents that the 3-and 5-positions of the phenyl group are substituted with carboxyl groups }, and the same is true for the other groups. Further, "naphthyl" means naphthyl, "NH-2 naphthyl (SO3H)3(3,6, 8)" means 3,6, 8-trisulfo-2 naphthylamino, "NH (cyclohexoxy)" means cyclohexylamino. In the following specific examples, the sulfo group may be in a salt state. And "M" although not described⁴"represents a hydrogen atom or a counter cation.

[ Table 1]

NO.	R₂₁、R₂₂	Xd	Y₂₁、Y₂₂
				2-0-1	CH3	Diamino ethylene radical	OH
2-0-2	CH3	Diamino ethylene radical	Cl
				2-0-3	CH3	Diamino ethylene radical	NH2
2-0-4	CH3	1, 4-piperazinediyl	Cl
				2-0-5	CH3	1, 4-piperazinediyl	NH2
2-0-6	CH3	1, 3-Diaminophendimethy	Cl
				2-0-7	CH3	1, 3-Diaminophendimethy	NH2
2-0-8	CH3	1, 4-Diaminophendimethy	NH2
				2-0-9	CH3	Bis (3-aminopropyl) ether	NH2
2-0-10	CH3	3, 3' -Iminobis (propylamine)	NH2
				2-0-11	CH3	2, 2' -Iminobis (ethylamine)	NH2
2-0-12	CH3	1, 4-diaminobutylene	NH2
				2-0-13	CH3	1, 6-diaminohexylidene	NH2
2-0-14	CH3	1, 4-diaminophenylene	NH2
				2-0-15	CH3	1, 3-diaminophenylene	NH2
2-0-16	CH3	1, 3-diamino-4-sulfophenylene	NH2
				2-0-17	CH3	1, 3-diamino-5-carboxyphenylene	NH2
2-0-18	CH3	4, 4' -diamino-2-sulfodiphenylamine	NH2

[ Table 2]

[ Table 3]

As the compound represented by the general formula (D), the following compounds are also preferable.

[ chemical formula 30]

The compound represented by the general formula (D) can be synthesized by a known synthesis method (for example, the synthesis method described in Japanese patent laid-open publication No. 2013-133396).

[ Compound represented by the general formula (E) ]

[ chemical formula 31]

Y₃₁Represents a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, or a morpholino group.

X₃₁Represents a group represented by the following general formula (E-1).

[ chemical formula 32]

In the general formula (E-1), R₃₂、R₃₃、R₃₄、R₃₅And R₃₆Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or-COOM '(M' represents a hydrogen atom or a counter cation). Wherein R is₃₂、R₃₃、R₃₄、R₃₅And R₃₆At least1 represents an alkyl group having 1 to 8 carbon atoms or-COOM'. Denotes a bond to a carbon atom.

When R is₃₁When an alkyl group is represented, the alkyl group may have a substituent. Specific examples and preferred ranges of alkyl groups and substituents and R in the general formula (D)₂₁The same is true.

As R₃₁From the viewpoint of availability of the raw material, a hydrogen atom or an unsubstituted alkyl group is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is even more preferable.

In the general formula (E), Y₃₁Represents a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, or a morpholino group

When Y is₃₁When an alkyl group is represented, the alkyl group may have a substituent. Specific examples and preferred ranges of amino groups and substituents and Y in the general formula (D)₂₁The same is true.

From the viewpoint of moisture resistance, Y is₃₁Preferably a chlorine atom, a hydroxyl group or an amino group, more preferably a hydroxyl group or an amino group, and still more preferably a hydroxyl group.

In the general formula (E), X₃₁Represents a group (substituted anilino group) represented by the general formula (E-1).

In the general formula (E-1), when R is₃₂、R₃₃、R₃₄、R₃₅And R₃₆When an alkyl group having 1 to 8 carbon atoms is used, the alkyl group having 1 to 8 carbon atoms is preferably a straight-chain or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a n-hexyl group, and a n-octyl group.

When the alkyl group is used, R is preferably selected in consideration of hue₃₂And R₃₆At least one of them is an alkyl group, and the others are hydrogen atoms. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.

M' represents a hydrogen atom or a counter cation. Examples of the counter cation include a 1-valent counter cation, preferably an alkali metal ion (preferably lithium ion, sodium ion, potassium ion, more preferably sodium ion), ammonium ion, and an organic cation. Examples of the organic cation include cations obtained by adding a hydrogen ion to an alkylamine or an alkanolamine, examples of the alkylamine include trimethylamine and triethylamine, and examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.

M' is preferably a hydrogen atom or an alkali metal ion.

As R₃₂～R₃₆Preferably an alkyl group having 1 to 8 carbon atoms or-COOM', preferably R₃₂～R ₃₆1 to 3 of these groups, more preferably 1 to 2 of these groups, and the others are hydrogen atoms.

When 2 of these are groups other than hydrogen atom, R is preferably₃₂And R₃₆Or R₃₃And R₃₅In the case of a group other than a hydrogen atom, when 3 are groups other than a hydrogen atom, R is preferably₃₂、R₃₄And R₃₆A group other than a hydrogen atom. More preferably R₃₂～R ₃₆1 to 3 of them are-COOM' and the others are hydrogen atoms. Further preferred is R₃₂、R₃₃Or R₃₅At least 1 of them is-COOM'.

As X₃₁Specific examples thereof include 2-methylanilino, 2, 6-dimethylanilino, 2, 5-dimethylanilino, 2,4, 6-trimethylanilino, 2, 6-diethylanilino, 2, 5-diethylanilino, 2, 6-diisopropylanilino, 2, 5-diisopropylanilino, 2-carboxyanilino, 3-carboxyanilino, 4-carboxyanilino, 2, 5-dicarboxyaninilino, 3, 5-dicarboxyaninilino, 5-carboxy-2-methylanilino, 5-carboxy-2-ethylanilino and the like.

X₃₁Preferably 2, 6-dimethylanilino, 2,4, 6-trimethylanilino, 2, 6-diethylanilino, 2, 6-diisopropylanilino, 2-carboxyanilino or3, 5-dicarboxylanilino, more preferably 2, 6-dimethylanilino, 2, 6-diethylanilino, 2, 6-diisopropylanilino, 2-carboxyanilino or3, 5-dicarboxylanilino, still more preferably 2-carboxyanilino or3, 5-dicarboxylanilino。

In the general formula (E), M⁵Represents a hydrogen atom or a counter cation. M⁵Each may be the same or different.

In the general formula (E), when M⁵In the form of a free acid when it is a hydrogen atom, when M is⁵In the form of a salt in the case of a counter cation.

Examples of the counter cation forming the salt include a counter cation having a valence of 1, and preferably include an alkali metal ion, an ammonium ion, an organic cation, and the like.

From the viewpoint of water solubility, alkali metal ions are preferred, and lithium ions, sodium ions, and potassium ions are more preferred. Sodium ions are particularly preferable from the viewpoint of inexpensive production.

In the above general formula (E), M⁵Each may be the same or different. That is, the form in which the compound represented by the general formula (E) is a salt includes a case in which all of the sulfo groups are in the form of a salt and a case in which a part of the sulfo groups are in the form of a free acid and a part of the sulfo groups are in the form of a salt. The counter cation forming the salt may be one kind or plural kinds.

Specific examples of the anthrapyridone compound represented by the general formula (E) are shown in the following table. In the table, (K) means "carboxyl", and 2(K) means "dicarboxyl". In the following specific examples, the carboxyl group may be in the form of a salt. And M is not described⁵Represents a hydrogen atom or a counter cation.

[ Table 4]

NO.	R₃₁	X₃₁	Y₃₁
				3-0-1	CH3	2, 6-dimethylanilino	OH
3-0-2	CH3	2, 6-dimethylanilino	NH2
				3-0-3	CH3	2, 5-dimethylanilino	OH
3-0-4	CH3	2-methylanilino group	OH
				3-0-5	CH3	2,4, 6-trimethylanilino	OH
3-0-6	CH3	2,4,6-Trimethylanilino radical	NH2
				3-0-7	H	2,4, 6-trimethylanilino	Cl
3-0-8	CH3	2,4, 6-trimethylanilino	2-ethylhexylamino group
				3-0-9	CH3	2, 6-diisopropylanilino	OH
3-0-10	CH3	2, 6-diisopropylanilino	NH2
				3-0-11	C2H5	2, 6-diisopropylanilino	Cl
3-0-12	CH3	2, 6-diisopropylanilino	Monoethanolamino
				3-0-13	CH3	2, 5-diIsopropyl phenylamino group	OH
3-0-14	CH3	2, 6-diethylanilino	OH
				3-0-15	CH3	2, 6-diethylanilino	NH2
3-0-16	CH3	2, 6-diethylanilino	Cl
				3-0-17	CH3	2, 6-diethylanilino	2-ethylhexylamino group
3-0-18	CH3	2, 6-diethylanilino	Monoethanolamino
				3-0-19	CH3	2, 6-diethylanilino	Diethanolamino group
3-0-20	C2H4OH	2,6-diethylanilino group	Morpholinyl radical
				3-0-21	CH3	2, 5-diethylanilino	OH
3-0-22	CH3	2, 5-diethylanilino	NH2
				3-0-23	CH3	2- (K) -anilino	OH
3-0-24	CH3	2- (K) -anilino	NH2
				3-0-25	CH3	2,5-2(K) -anilino	OH
3-0-26	C4H9	2,5-2(K) -anilino	NH2
				3-0-27	CH3	3,5-2(K) -anilino	OH
3-0-28	CH3	3- (K) -anilino	OH
				3-0-29	CH3	4- (K) -anilino	OH
3-0-30	CH3	5- (K) -2-methylanilino	OH
				3-0-31	CH3	5- (K) -2-ethylanilino	OH
3-0-32	CH3	2, 5-diisopropylanilino	Cl
				3-0-33	CH3	2,4, 6-trimethylanilino	Cl
3-0-34	CH3	2- (K) -anilino	Cl
				3-0-35	CH3	3,5-2(K) -anilino	Cl
3-0-36	CH3	4- (K) -anilino	Cl
				3-0-37	CH3	3- (K) -anilino	Cl

The compound represented by the general formula (E) can be synthesized by a known synthesis method (for example, the synthesis method described in Japanese patent laid-open publication No. 2013-133396).

[ coloring composition ]

The coloring composition of the present invention comprises the compound represented by the above general formula (1) and at least one compound selected from the group consisting of the compound represented by the above general formula (D) and the compound represented by the above general formula (E).

The compound represented by the above general formula (1) contained in the coloring composition of the present invention may be one kind, or two or more kinds. The coloring composition of the present invention may contain one or more compounds represented by the above general formula (D) and one or more compounds represented by the above general formula (E).

The coloring composition of the present invention may contain a medium, but is particularly suitable as an ink for inkjet recording when a solvent is used as the medium. The coloring composition of the present invention can be produced by using a lipophilic medium or an aqueous medium as a medium, and dissolving and/or dispersing the compound represented by the general formula (1). The aqueous medium is preferably used. The coloring composition of the present invention further contains a composition for ink other than the medium.

The content (W) of the compound represented by the general formula (1) contained in the coloring composition₁) The content of the compound represented by the general formula (1) in the coloring composition is preferably 1.5 to 20.0% by mass, more preferably 1.5 to 10.0% by mass, further preferably 1.5 to 5.0% by mass, particularly preferably 2.0 to 5.0% by mass, and most preferably less than 2.5% by mass and less than 5.0% by mass, based on the total mass of the coloring composition, although the content is determined depending on the kind of the compound represented by the general formula (1) used, the kind of the solvent component used for producing the coloring composition, and the like.

The content (W) of the compound represented by the above general formula (D) contained in the coloring composition_D) And the content (W) of the compound represented by the above general formula (E)_E) Total (W) of_D+W_E) The amount of the coloring composition is preferably 0.1 to 10.0% by mass, more preferably 0.1 to 8.0% by mass, even more preferably 0.1 to 5.0% by mass, and most preferably 0.1 to 3.0% by mass, based on the total mass of the coloring composition.

The content (W) of the compound represented by the general formula (1) contained in the coloring composition₁) The content (W) of the compound represented by the general formula (D)_D) And the content (W) of the compound represented by the above general formula (E)_E) Total content (W) of₁+W_D+W_E) Preferably 1.0 to 10.0 mass%, more preferably 1.0 to 8.0 mass%, further preferably 1.5 to 6.0 mass%, particularly preferably 1.0 to 5.0 mass%, and most preferably 2.0 to 5.0 mass%.

By mixing W₁+W_D+W_EThe ink concentration of the ink on the recording medium at the time of printing can be made good by making the ink concentration 2.0 mass% or more. And, by mixing W₁+W_D+W_EWhen the amount is 5.0 mass% or less, the effect that the discharge property of the coloring composition in the case of using the inkjet recording method can be improved and the inkjet nozzle is less likely to be clogged can be obtained.

Slave colorIn view of the balance among the phase, chroma, tinctorial strength (print density), light fastness, ozone fastness and moisture resistance, W is the mass ratio of the content of the compound represented by the general formula (1) to the sum of the content of the compound represented by the general formula (D) and the content of the compound represented by the general formula (E)₁/(W_D+W_E) The mass ratio of (A) is preferably 99/1-1/99, more preferably 99/5-50/50, more preferably 95/5-50/50, still more preferably 90/10-50/50, and particularly preferably 90/10-60/40.

The coloring composition of the present invention may contain other additives as needed within the range that exhibits the effects of the present invention. The coloring composition of the present invention is suitably used as an ink for inkjet recording.

[ ink for ink-jet recording ]

The ink for inkjet recording can be produced by dissolving and/or dispersing the compound represented by the general formula (1) and at least one compound selected from the group consisting of the compound represented by the general formula (D) and the compound represented by the general formula (E) in a lipophilic medium or an aqueous medium. The ink for inkjet recording is preferably an ink using an aqueous medium.

The preferable ranges of the content of the compound represented by the general formula (1), the content of the compound represented by the general formula (D), the content of the compound represented by the general formula (E), and the mass ratio of the content of the compound represented by the general formula (1) to the total content of the compound represented by the general formula (D) and the compound represented by the general formula (E) in the ink for inkjet recording are the same as those described above.

The ink for inkjet recording may contain other additives as needed within the range in which the effects of the present invention are exhibited. Examples of the other additives include known additives such as an anti-drying agent (wetting agent), an anti-fading agent, an emulsion stabilizer, a permeation enhancer, an ultraviolet absorber, a preservative, a fungicide, a pH adjuster, a surface tension adjuster, an antifoaming agent, a viscosity adjuster, a dispersant, a dispersion stabilizer, a rust inhibitor, a chelating agent, and a betaine compound. These various additives can be directly added to the ink liquid in the case of a water-soluble ink. When the oil-soluble dye is used in the form of a dispersion, it is usually added to the dispersion after the dye dispersion is prepared, but it may be added to an oil phase or an aqueous phase during the preparation.

The anti-drying agent is suitably used for the purpose of preventing clogging of an ink ejection orifice of a nozzle used in an ink jet recording system due to drying of an ink for ink jet recording.

The drying-preventing agent is preferably a water-soluble organic solvent having a lower vapor pressure than water. Specific examples thereof include polyhydric alcohols typified by ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1, 3-propanediol, 1,2, 6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane and the like, ethylene glycol monomethyl (or ethyl) ether, lower alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl (or ethyl) ether and triethylene glycol monoethyl (or butyl) ether, heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and N-ethylmorpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, and 3-sulfolene, polyfunctional compounds such as diacetone alcohol and diethanolamine, and urea derivatives. Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. The above-mentioned drying-preventing agents may be used alone or in combination of two or more. The anti-drying agent is preferably contained in the ink in an amount of 10 to 50% by mass.

The penetration enhancer can be used for the purpose of allowing the ink for inkjet recording to better penetrate into paper. Examples of the permeation enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether and 1, 2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. These ink compositions usually have sufficient effects when contained in an amount of 5 to 30% by mass, and are preferably used in an amount within a range that does not cause print bleeding or print-through (printthrough).

The ultraviolet absorber can be used for the purpose of improving the storage stability of an image. As the ultraviolet absorber, a benzotriazole-based compound disclosed in, for example, Japanese patent application laid-open Nos. 58-185677, 61-190537, 2-782, 5-197075, 9-34057, 46-2784, 5-194483, 3214463, benzophenone-based compound disclosed in, for example, Japanese patent application laid-open No. 48-30492, 56-21141, 10-88106, cinnamic acid-based compound disclosed in, for example, Japanese patent application laid-open Nos. 4-298503, 8-53427, 8-239368, 10-182621, etc, Triazine compounds described in Japanese patent application laid-open No. 8-501291 and the like, compounds described in research DisclosureNo.24239, compounds which absorb ultraviolet rays and emit fluorescence, such as stilbene compounds and benzoxazole compounds, and so-called fluorescent whitening agents.

The fading inhibitor is used for the purpose of improving the preservability of an image. As the fading inhibitor, various organic or metal complex fading inhibitors can be used. Organic discoloration inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, and the like, and metal complexes include nickel complexes, zinc complexes, and the like. More specifically, compounds described in the patent cited in Research disclosureno.15162, Research disclosureno. 18716, on the left column of 650, 527, 872, 15162, 127 of Research disclosureno.15162, or representative compounds described in japanese patent laid-open publication No. sho.62-215272, general formulae of the compounds and compounds contained in examples of the compounds can be used.

Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium mercaptopyridine-1-oxide, ethyl p-hydroxybenzoate, 1, 2-benzisothiazolin-3-one and salts thereof. These are preferably used in an amount of 0.02 to 1.00% by mass in the ink.

As the pH adjuster, the above-mentioned neutralizing agent (organic base, inorganic base) can be used. The pH adjuster is preferably added so that the pH of the ink for ink jet recording becomes 6 to 10, more preferably 7 to 10, for the purpose of improving the storage stability of the ink for ink jet recording.

Examples of the surface tension adjusting agent include nonionic, cationic, and anionic surfactants. The ink for inkjet recording of the present invention preferably has a surface tension of 25 to 70 mN/m. More preferably 25 to 60 mN/m. The viscosity of the ink for inkjet recording of the present invention is preferably 30mPa · s or less. Further, it is more preferably adjusted to 20 mPas or less. Examples of the surfactant include anionic surfactants such as fatty acid salts, alkylsulfuric acid ester salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, dialkylsulfosuccinic acid salts, alkylphosphoric acid ester salts, naphthalenesulfonic acid formalin condensates, and polyoxyethylene alkylsulfuric acid ester salts, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylallyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and ethylene oxide-propylene oxide block copolymers. In addition, SURFYNOLS (air products & Chemicals) which is an acetylene based polyoxyethylene oxide surfactant is also preferably used. Further, an amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferable. Further, those listed as surfactants described in Japanese patent application laid-open No. 59-157,636, pages (37) to (38), research disclosure No.308119 (1989), can also be used.

As the defoaming agent, a fluorine-based or silicone-based compound, a chelating agent typified by EDTA, or the like can be used as necessary.

The betaine compound can be used for the purpose of preventing bleeding of an image under high humidity conditions. As the betaine compound, those exemplified in Japanese patent laid-open publication No. 2004-285269 and the like can be preferably used. The preferable range of the addition amount of these betaine compounds varies depending on the kind thereof, and 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, and most preferably 0.01 to 3.0% by mass is used in the ink for inkjet recording.

The aqueous medium may be a mixture containing water as a main component and, if desired, a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexylene glycol, pentanediol, glycerol, hexanetriol, thiodiglycol), glycol derivatives (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), and the like, Amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (e.g., formamide, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidinone, 1, 3-dimethyl-2-imidazolidinone, acetonitrile, acetone). Two or more water-miscible organic solvents may be used simultaneously.

The viscosity of the ink for inkjet recording of the present invention is preferably 30mPa · s or less. The surface tension is preferably 25mN/m or more and 70mN/m or less. The viscosity and surface tension can be adjusted by adding various additives, for example, a viscosity adjuster, a surface tension adjuster, a specific resistance adjuster, a coating adjuster, an ultraviolet absorber, an antioxidant, a discoloration inhibitor, a mold inhibitor, a rust inhibitor, a dispersant, and a surfactant.

The ink for inkjet recording of the present invention can be used for inks of various hues, and is preferably used for inks of magenta hue. Further, the present invention can be used not only for monochromatic image formation but also for full-color image formation. For forming a full-color image, magenta color tone ink, cyan color tone ink, and yellow color tone ink can be used, and black color tone ink can be used for adjusting the color tone.

The ink for ink jet recording of the present invention can be used in recording methods such as printing, copying, marking, note-making, drawing, and imprinting, and is particularly suitable for use in ink jet recording methods.

[ ink jet recording method ]

In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording of the present invention, an image is formed on a known image receiving material, that is, plain paper or resin-coated paper, for example, inkjet special paper, a film, an electrophotographic paper, a fabric, glass, metal, ceramics, and the like described in japanese patent application laid-open nos. 8-169172, 8-27693, 2-276670, 7-276789, 9-323475, 62-238783, 10-153989, 10-217473, 10-235995, 10-337947, 10-217597, and 10-337947.

In the formation of an image, a polymer fine particle dispersion (also referred to as a polymer latex) may be used together for the purpose of imparting gloss and water resistance or improving weather resistance. The timing of applying the polymer latex to the image receiving material may be before or after applying the colorant, or may be simultaneous with applying the colorant, and therefore, the place to be added may be in the image receiving paper, in the ink, or may be used as a liquid substance of the polymer latex alone. Specifically, the methods described in the respective specifications of Japanese patent application No. 2000-363090, Japanese patent application No. 2000-315231, Japanese patent application No. 2000-354380, Japanese patent application No. 2000-343944, Japanese patent application No. 2000-268952, Japanese patent application No. 2000-299465, Japanese patent application No. 2000-297365 and the like can be preferably used.

[ ink-jet printer ink cartridge and ink-jet recorded matter ]

The ink cartridge for inkjet recording of the present invention is filled with the ink for inkjet recording of the present invention. The ink jet recorded matter is formed into a colored image on a recording medium by using the ink for ink jet recording of the present invention.

The ink for ink jet recording of the present invention is not limited to the ink jet recording method, and can be used in known methods such as a charge control method in which ink is ejected by electrostatic attraction, a drop-on-demand method (pressure pulse method) in which vibration pressure of a piezoelectric element is used, an acoustic ink jet method in which an ink is irradiated with an electric signal converted into an acoustic beam and ejected by radiation pressure, and a thermal ink jet method in which ink is heated to form bubbles and the generated pressure is used. The inkjet recording system includes a system in which a large amount of ink having a low density, which is called photo ink, is ejected in a small volume, a system in which a plurality of inks having substantially the same hue and different densities are used to improve image quality, and a system in which colorless transparent ink is used.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "%" and "part(s)" are% by mass and part(s) by mass unless otherwise specified.

(Synthesis example) (Synthesis of exemplary Compound (1-11))

The exemplified compounds (1 to 11) can be synthesized, for example, according to the following scheme.

[ chemical formula 33]

[ chemical formula 34]

(Synthesis of sulfonylfluorescein)

76.4g of saccharin and 100g of concentrated sulfuric acid were added to a 1L 3-neck flask at room temperature (20 ℃ C.), and the mixture was warmed to 120 ℃. 200g of sulfolane and 103.3g of resorcinol were added. The mixture after the addition was warmed to 140 ℃ and stirred at 140 ℃ for 20 hours. Then, the obtained reaction solution was cooled to 20 ℃ over 1 hour. 500g of water was added to the cooled reaction solution over 30 minutes, and the mixture was stirred for a further 30 minutes. The resulting suspension was filtered and the resulting crystals were spray-washed 4 times with 130mL of water. The spray-washed crystals were air-dried at 50 ℃ for 20 hours, whereby 68.5g of sulfonylfluorescein was obtained as yellow crystals (yield 45%).

(Synthesis of DCSF)

A200 mL 3-neck flask was charged with 36.8g of sulfonylfluorescein and 150g of phosphorus oxychloride. The mixture was warmed to 105 ℃ and stirred at 105 ℃ for 18 hours. Then, it was cooled to 20 ℃ over 1 hour. To a 2L three-necked flask to which 1L of water was added, the obtained reaction solution was added over 20 minutes while cooling the flask in a water bath at 20 ℃ so that the water temperature did not exceed 35 ℃. After the addition, the mixture was stirred at 20 ℃ for 1 hour. The resulting suspension was filtered, and the crystals were washed 1 time with 200mL of water followed by 2 times with 200mL of acetonitrile. The washed crystals were air-dried at 50 ℃ for 18 hours, whereby 22.7g of Dichlorosulfophthalein (DCSF) was obtained (yield 56%).

(Synthesis of intermediate (A))

30g of Dichlorosulfonephthalein (DCSF), 63g of 2,4, 6-trimethyl-1, 3-phenylenediamine (Tokyo Chemical Industry Co., Ltd.) and 11g of zinc chloride were added to 265g of ethylene glycol, and reacted at 150 ℃ for 6 hours. The reaction mixture was cooled to room temperature, 300mL of 0.6mol/L hydrochloric acid was added dropwise to precipitate crystals, and the precipitated crystals were filtered and washed with 300mL of water. The obtained crystals were dried at 60 ℃ for 12 hours to obtain crystals of intermediate (a). Yield 23g, 50% yield, ms spectrum (M S) (M/z) 633([ M +1] +, 100%).

(Synthesis of intermediate (B))

23.0g of intermediate (A) was added to 420g of 10% oleum, andthe reaction was carried out at room temperature for 48 hours. The reaction solution was poured into a large excess of ethyl acetate, and the precipitated crystals were filtered. The filtered crystals were dissolved in 500mL of methanol, adjusted to pH7 using 28% sodium methoxide methanol solution, and the precipitated sodium sulfate was removed by filtration. The filtrate was concentrated using a rotary evaporator, and the obtained residue was purified by column chromatography (packing material: Sephadex LH-20 (Pharmacia), developing solvent: methanol) to obtain crystals of intermediate (B). Yield 21.0g, 68% yield, Mass Spectrum (MS) (M/z) 793([ M-2Na + H)]^-、100％)。

(Synthesis of exemplary Compound (1-11))

3.0g of intermediate (B) was dissolved in 15mL of ultrapure water, and the internal temperature was cooled to 10 ℃ or lower. 2.55g of 5-chlorosulfonylsalicylic acid (synthesized by the method described in German patent DE 264786) was added in the form of powder, and the reaction mixture was kept at pH 8.0 by using a 10% aqueous NaOH solution at an internal temperature of 10 ℃ or lower as it is, and was continuously added dropwise until the pH did not change. The obtained reaction solution was poured into a large excess of isopropyl alcohol, and the precipitated solid was filtered. The resulting solid was dissolved in water/methanol: 1/1 was mixed with 20mL of a solvent, and after purification by column chromatography (packing material: Sephadex LH-20 (Pharmacia), developing solvent: water/methanol), inorganic salts and the remaining organic solvent were removed by using a Dialysis Membrane (molecular weight fraction 3500, Spectrum a/Por3 analysis Membrane (trade name, Spectrum Laboratories, Inc.)). The pH of the obtained aqueous solution was adjusted to 7 with a dilute aqueous sodium hydroxide solution, and the solution was subjected to dust removal filtration with a membrane filter, and the obtained aqueous solution was concentrated, dried and solidified with a rotary evaporator to obtain green glossy crystals of the exemplified compound (1-11). Yield 1.5g, 33% yield. MS (M/z) ═ 1191([ M-1 ]]^-100%). The absorption maximum wavelength of the absorption spectrum in a diluted aqueous solution of the exemplary compound (1-11) was 532nm, and the molar absorption coefficient was 87000. The compound (1-11) exemplified above was added to dimethyl sulfoxide-d 6¹The H-NMR spectrum is shown in FIG. 1.

(Synthesis of exemplary Compound (1-18))

The exemplified compounds (1 to 18) can be synthesized, for example, according to the following scheme.

[ chemical formula 35]

3.0g of intermediate (B) obtained as a synthesis intermediate of the above exemplified compound (1-11) was dissolved in 15mL of ultrapure water, and the internal temperature was cooled to 10 ℃ or lower. 2.2g of 5-chlorosulfonyl-3-hydroxy-2-naphthoic acid (synthesized by the method described in DE 264786) was added in the form of powder, and the reaction mixture was kept at pH 7.5 with a 10% aqueous NaOH solution at an internal temperature of 10 ℃ or lower, and was continuously added dropwise until the pH did not change. The obtained reaction solution was poured into a large excess of isopropyl alcohol, and the precipitated solid was filtered. The resulting solid was dissolved in water/methanol: 1/1 in 20mL of a mixed solvent, and after purification by column chromatography (packing material: Sephadex LH-20 (Pharmacia), developing solvent: water/methanol), inorganic salts and the remaining organic solvent were removed by using a dialysis Membrane (fraction molecular weight 3500, Spectra/Por3 Di analysis Membrane (trade name, Spectrum Laboratories, Inc.)). The pH of the obtained aqueous solution was adjusted to 7 using a dilute aqueous sodium hydroxide solution, and the obtained aqueous solution was subjected to dust removal filtration using a membrane filter, and concentrated, dried and solidified using a rotary evaporator to obtain green glossy crystals of the exemplified compounds (1 to 18). Yield 1.2g, 24%. MS (M/z) ═ 1291([ M-1 ]]^-100%). The absorption maximum wavelength of the absorption spectrum in a diluted aqueous solution of the exemplified compounds (1 to 18) was 532nm, and the molar absorption coefficient was 85000. The compound (1-18) exemplified above was added to dimethyl sulfoxide-d 6¹The H-NMR spectrum is shown in FIG. 2.

(Synthesis of exemplary Compound (1-25))

The exemplified compounds (1 to 25) can be synthesized, for example, according to the following scheme.

[ chemical formula 36]

3.0g of intermediate (B) obtained as a synthesis intermediate of the above exemplified compound (1-11) was dissolved in 15mL of ultrapure water, and the internal temperature was cooled to 10 ℃ or lower. 2.2g of 6-chlorosulfonyl-2-hydroxy-1-naphthoic acid (synthesized by the method described in DE 278091) was added in the form of powder, and the reaction mixture was kept at pH 7.5 with a 10% aqueous NaOH solution at an internal temperature of 10 ℃ or lower, and was continuously added dropwise until the pH did not change. The obtained reaction solution was poured into a large excess of isopropyl alcohol, and the precipitated solid was filtered. The resulting solid was dissolved in water/methanol: 1/1 in 20mL of a mixed solvent, and after purification by column chromatography (packing material: Sephadex LH-20 (Pharmacia), developing solvent: water/methanol), inorganic salts and the remaining organic solvent were removed by using a dialysis Membrane (fraction molecular weight 3500, Spectra/Por3 Di analysis Membrane (trade name, Spectrum Laboratories, Inc.)). The pH of the obtained aqueous solution was adjusted to 7 using a dilute aqueous sodium hydroxide solution, and the obtained aqueous solution was subjected to dust removal filtration using a membrane filter, and concentrated, dried and solidified using a rotary evaporator to obtain green glossy crystals of the exemplified compound (1-25). Yield 1.3g, 26%. MS (M/z) ═ 1291([ M-1 ]]^-100%). The absorption maximum wavelength of the absorption spectrum in a diluted aqueous solution of the exemplified compounds (1 to 25) was 532nm, and the molar absorption coefficient was 83000.

(Synthesis of exemplary Compound (1-26))

The exemplified compounds (1 to 26) can be synthesized, for example, according to the following scheme.

[ chemical formula 37]

3.0g of intermediate (B) obtained as a synthesis intermediate of the above exemplified compound (1-11) was dissolved in 15mL of ultrapure water, and the internal temperature was cooled to 10 ℃ or lower. 2.7g of 5-chlorosulfonyl-4-hydroxyisophthalic acid (synthesized by the method described in DE 264786) was added in the form of powder, and a 10% aqueous NaOH solution was directly used at an internal temperature of 10 ℃ or lowerThe pH of the reaction solution was maintained at 7.5, and the dropwise addition was continued until the pH was unchanged. The obtained reaction solution was poured into a large excess of isopropyl alcohol, and the precipitated solid was filtered. The resulting solid was dissolved in water/methanol: 1/1 in 20mL of a mixed solvent, and purifying the mixture by column chromatography (packing material: Sephadex LH-20 (Pharmacia), developing solvent: water/methanol), inorganic salts and the remaining organic solvent were removed by using a Dialysis Membrane (fraction molecular weight 3500, Spectr a/Por3 analysis Membrane (trade name, Spectrum Laboratories, Inc.)). The pH of the obtained aqueous solution was adjusted to 7 using a dilute aqueous sodium hydroxide solution, and the obtained aqueous solution was subjected to dust removal filtration using a membrane filter, and concentrated, dried and solidified using a rotary evaporator to obtain green glossy crystals of the exemplified compounds (1 to 26). Yield 1.8g, 36%. MS (M/z) ═ 1279([ M-1 ]]^-100%). The absorption maximum wavelength of the absorption spectrum in a diluted aqueous solution of the exemplified compounds (1 to 26) was 534nm, and the molar absorption coefficient was 95000. The compound (1-26) exemplified above was added to dimethyl sulfoxide-d 6¹The H-NMR spectrum is shown in FIG. 3.

(Synthesis of exemplary Compound (1-30))

The exemplified compounds (1 to 30) can be synthesized, for example, according to the following scheme.

[ chemical formula 38]

3.0g of intermediate (B) obtained as a synthesis intermediate of the above exemplified compounds (1-11) was dissolved in 15mL of ultrapure water. 2.2g of 5-chlorosulfonyl-isophthalic acid dimethyl ester (synthesized by the method described in DE 278091) was added in the form of powder, and the reaction solution was kept at pH 5 to 7 with a 10% NaOH aqueous solution and was continuously added dropwise until the pH did not change. After the reaction was completed, 3mL of 50% aqueous NaOH solution was added and the mixture was stirred for 1 hour. The obtained reaction solution was poured into a large excess of isopropyl alcohol, and the precipitated solid was filtered. The resulting solid was dissolved in water/methanol: 1/1 mixed solvent 20mL, and column colorAfter purification by chromatography (filler: Sephadex LH-20 (Pharmacia), developing solvent: water/methanol), inorganic salts and the remaining organic solvent were removed using a Dialysis Membrane (molecular weight fraction 3500, Spectra/Por3 analysis Membrane (trade name, Spectrum Laboratories, Inc.)). The pH of the obtained aqueous solution was adjusted to 7 using a dilute aqueous sodium hydroxide solution, and the obtained aqueous solution was subjected to dust removal filtration using a membrane filter, and concentrated, dried and solidified using a rotary evaporator to obtain green glossy crystals of the exemplified compound (1-30). Yield 3.7g, yield 70%. MS (M/z) ═ 1247([ M-1 ]]^-100%). The absorption maximum wavelength of the absorption spectrum in a diluted aqueous solution of the exemplified compounds (1 to 30) was 532nm, and the molar absorption coefficient was 82000. The compound (1-30) exemplified above was added to dimethyl sulfoxide-d 6¹The H-NMR spectrum is shown in FIG. 4.

Other exemplary compounds can be synthesized according to the methods described above.

The following compound (d-1) was synthesized with reference to Japanese patent application laid-open No. 2003-192930, and (e-1) was synthesized with reference to International publication No. 04/104108. Other exemplary compound (d-2) and exemplary compound (d-3) can also be synthesized by the above-described method.

[ chemical formula 39]

[ chemical formula 40]

[ example 1]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20 μm to prepare an ink for magenta ink jet recording 1. The compound of the general formula (1) represents a compound represented by the general formula (1), the compound of the general formula (D) represents a compound represented by the general formula (D), and the compound of the general formula (E) represents a compound represented by the general formula (E).

[ example 2]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 2 for magenta.

[ chemical formula 41]

[ example 3]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 3 for magenta.

[ chemical formula 42]

[ example 4]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink for magenta ink jet recording 4.

[ example 5]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 5 for magenta.

[ example 6]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 6 for magenta.

[ example 7]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink 7 for magenta ink jet recording.

[ example 8]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 8 for magenta.

[ example 9]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink 9 for magenta ink jet recording.

[ example 10]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink for magenta ink jet recording 10.

[ example 11]

An ink 11 for inkjet recording was prepared in the same manner as in example 2, except that the exemplary compounds (1 to 18) were used instead of the exemplary compounds (1 to 11).

[ example 12]

An ink 12 for inkjet recording was prepared in the same manner as in example 2, except that the exemplary compounds (1 to 19) were used instead of the exemplary compounds (1 to 11).

[ example 13]

An ink for inkjet recording 13 was prepared in the same manner as in example 2, except that the exemplary compounds (1 to 20) were used instead of the exemplary compounds (1 to 11).

[ example 14]

An ink for inkjet recording 14 was prepared in the same manner as in example 2, except that the exemplary compounds (1) to (25) were used instead of the exemplary compounds (1) to (11).

[ example 15]

An ink for inkjet recording 15 was prepared in the same manner as in example 1, except that the exemplary compounds (1 to 26) were used instead of the exemplary compounds (1 to 11).

[ example 16]

An ink 16 for inkjet recording was prepared in the same manner as in example 2, except that the exemplary compounds (1 to 26) were used instead of the exemplary compounds (1 to 11).

[ example 17]

An ink 17 for inkjet recording was prepared in the same manner as in example 2, except that the exemplary compounds (1 to 29) were used instead of the exemplary compounds (1 to 11).

[ example 18]

An ink 18 for inkjet recording was prepared in the same manner as in example 1, except that the exemplary compounds (1 to 30) were used instead of the exemplary compounds (1 to 11).

[ example 19]

An ink 19 for inkjet recording was prepared in the same manner as in example 2, except that the exemplary compounds (1 to 30) were used instead of the exemplary compounds (1 to 11).

[ example 20]

An ink for inkjet recording 20 was prepared in the same manner as in example 2, except that the exemplary compounds (1 to 34) were used instead of the exemplary compounds (1 to 11).

[ example 21]

An ink for inkjet recording 21 was prepared in the same manner as in example 1, except that the exemplary compounds (1 to 35) were used instead of the exemplary compounds (1 to 11).

[ example 22]

An ink 22 for inkjet recording was prepared in the same manner as in example 2, except that the exemplary compounds (1 to 35) were used instead of the exemplary compounds (1 to 11).

[ example 23]

An ink 23 for inkjet recording was prepared in the same manner as in example 1, except that the example compound (d-2) was used instead of the example compound (d-1).

[ example 24]

An ink 24 for inkjet recording was prepared in the same manner as in example 2, except that the example compound (d-3) was used instead of the example compound (d-1).

[ example 25]

An ink 25 for inkjet recording was prepared in the same manner as in example 2, except that the example compound (e-1) was used instead of the example compound (d-1).

[ example 26]

An ink 26 for inkjet recording was prepared in the same manner as in example 16, except that the example compound (d-2) was used instead of the example compound (d-1).

[ example 27]

An ink for inkjet recording 27 was prepared in the same manner as in example 19, except that the example compound (d-3) was used instead of the example compound (d-1).

[ example 28]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 28 for magenta.

[ example 29]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 29 for magenta.

[ example 30]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink for magenta ink jet recording 30.

[ example 31]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 31 for magenta.

[ example 32]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink 32 for magenta ink jet recording.

[ example 33]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 33 for magenta.

[ example 34]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 34 for magenta.

[ example 35]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare an ink-jet recording ink 35 for magenta.

[ comparative example 1]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 1 for magenta.

[ comparative example 2]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 2 for magenta.

[ comparative example 3]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 3 for magenta.

[ comparative example 4]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to obtain a comparative ink-jet recording ink 4 for magenta.

[ comparative example 5]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 5 for magenta.

[ comparative example 6]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to obtain a comparative ink-jet recording ink 6 for magenta.

[ comparative example 7]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 7 for magenta.

[ comparative example 8]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 8 for magenta.

[ comparative example 9]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 9 for magenta.

[ comparative example 10]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 10 for magenta.

[ comparative example 11]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 11 for magenta.

[ comparative example 12]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 12 for magenta.

[ comparative example 13]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative inkjet recording ink 13 for magenta.

[ comparative example 14]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to obtain a comparative inkjet recording ink 14 for magenta.

[ comparative example 15]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 15 for magenta.

[ comparative example 16]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 16 for magenta.

[ comparative example 17]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 17 for magenta.

[ comparative example 18]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 18 for magenta.

[ comparative example 19]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 19 for magenta.

[ comparative example 20]

Deionized water was added to the components described below to make 100g, and then the mixture was stirred for 1 hour while heating at 30 to 40 ℃. Then, the pH was adjusted to 8.5 with a 10mol/L aqueous solution of sodium hydroxide, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.20. mu.m, to prepare a comparative ink-jet recording ink 20 for magenta.

[ chemical formula 43]

[ chemical formula 44]

(image recording and evaluation)

Using the ink for inkjet recording prepared in the above, image recording was performed as follows to evaluate. In each of the examples and comparative examples, image recording was performed by a combination of an ink jet printer and recording paper as described below, and evaluation was performed.

The following evaluations were made with respect to the inks for inkjet recording 1 to 27 of the examples and the comparative inks for inkjet recording 1 to 11 of the comparative examples. The results are shown in tables 5 and 6.

In tables 5 and 6, the ink jet recording inks were loaded into the ink cartridges and images were recorded on photographic paper (Seiko Eps on corp. photographic paper < gloss) with an ink jet printer (Seiko Epson corp.; PM-700C) before evaluation.

The following evaluations were made with respect to the inks 28 to 35 for inkjet recording of examples and the comparative inks 12 to 20 for inkjet recording of comparative examples. The results are shown in Table 6. In table 6, each ink for inkjet recording was loaded into an ink cartridge, and an image was recorded on an inkjet special paper (manufactured by Canon inc.; glossy photo paper PT-201) by an inkjet printer (manufactured by Canon inc.; PIXUS Pro9000MkI I) and then evaluated.

< color phase >

The printed sample was visually observed, and the case of pure magenta, magenta with reddish color close to red, and C were evaluated in three stages.

Colour intensity

The chroma (C) of the printed matter according to the color characteristics and by the following formula^*) The calculation is performed. The CIE L was measured for the portion of the printed image at 50% applied voltage using a reflectance densitometer (trade name X-Rite310TR, manufactured by X-Rite Inc.)^*a^*b^*Lightness L in the color system (International Commission on illumination Standard (1976) or JIS (Japanese Industrial Standard) Z8781-4: 2013)^*And chroma a^*And b^*Then, the chroma (C) is calculated from the obtained value according to the following calculation formula^*) Then, evaluation was performed according to the following criteria.

[ numerical formula 1]

Chroma (C)^*)＝(a^*2+b^*2)^1/2

A：C^*When it is more than 90

B：C^*80 or more and less than 90

C：C^*Less than 80 times

< printing density >

By the combination of the ink jet printer and the recording paper, a full-surface coated image (a printed image at an applied voltage of 100%) was recorded using each ink for ink jet recording.

The print density of the entire surface coating image obtained was measured using a reflection densitometer (trade name X-Rite310TR, manufactured by X-Rite inc.), and the case where the print density was 2.0 or more was evaluated as a, the case where the print density was 1.8 or more and less than 2.0 was evaluated as B, the case where the print density was 1.7 or more and less than 1.8 was evaluated as C, and the case where the print density was less than 1.7 was evaluated as D in four stages.

< light resistance >

After the image density Ci immediately after recording was measured, the image was irradiated with 28 days xenon light (10 million lux) using a weatherometer (map c.165), the image density Cf1 was measured again, and the residual dye ratio was calculated from the image densities before and after xenon light irradiation, and evaluated. The image density was measured using a reflection densitometer (trade name X-Rite310TR, manufactured by X-Rite Inc.). The residual dye ratio was measured using an image portion having an initial image density of 1.0 ± 0.2.

The residual dye ratio was determined by the following formula, and the light resistance was evaluated based on the following criteria.

Residual dye ratio (%) (Cf1/Ci) × 100

A: when the residual rate of the pigment is 90% or more and less than 95%

B: when the residual rate of the pigment is 80% or more and less than 90%

C: when the residual rate of pigment is less than 80%

< ozone resistance >

The recording paper on which an image was formed was left to stand for 3 days In a box set In a dark place with an ozone gas concentration of 5 + -0.1 ppm at room temperature while applying a 5kV AC voltage while passing dry air through a double glass tube of a Siemens-type ozone generator, the image concentration after the ozone gas was left to stand was measured using a reflection densitometer (trade name X-Rite310TR, manufactured by X-Rite Inc.), and the residual pigment ratio was calculated from the initial image concentration Ci and the image concentration Cf2 after the ozone gas was left to stand, and evaluated. The residual dye ratio was measured using an image portion having an initial image density of 1.0 ± 0.2. The ozone gas concentration in the tank was set using an APPLICS CORP ozone gas monitor (model: OZG-EM-01).

The residual dye ratio was determined by the following formula, and the ozone resistance was evaluated by the following criteria.

Residual dye ratio (%) (Cf2/Ci) × 100

A: when the residual rate of the pigment is 85% or more and less than 90%

B: when the residual rate of the pigment is 80% or more and less than 85%

C: when the residual rate of pigment is less than 80%

< moisture resistance >

Regarding bleeding of an image under high humidity conditions, a 1mm × 1mm square of magenta was arranged so that a 0.5mm white background gap was formed between the squares, and a 3cm × 3cm printed pattern was prepared, and this image sample was stored at 45 ℃ under a relative humidity of 80% for 7 days, and then, the bleeding of the magenta dye in the white background gap was observed.

Specifically, OD values of a printed matter before exposure to the above conditions (45 ℃ C., relative humidity 80% of the printed matter) and after storage for 7 days under the above conditions were measured using a reflection densitometer "Spectrilino" (product name: manufactured by Gretag Co.), and the increase in magenta concentration against a white background immediately after printing and after storage for 7 days under the above conditions was measured in a green filter in state A, where A is a case where the concentration is less than 0.02, B is a case where the concentration is 0.02 to less than 0.05, C is a case where the concentration is 0.05 to less than 0.10, and D is a case where the concentration is 0.10 or more.

< spitting stability >

First, immediately after each ink for inkjet recording was prepared, the discharge of ink from all the nozzles of the inkjet printer was confirmed by the combination of the inkjet printer and the recording paper. Then, the sheet was output to 100 sheets of recording paper, and evaluation was performed according to the following criteria, and as a result, the evaluation result was "a" in all examples and comparative examples. In addition, a4 paper was used for the size of the recording paper.

Next, after each ink for inkjet recording was kept at 40 ℃ and a relative humidity of 80% for 2 weeks, the inkjet printer and the recording paper (size of recording paper a4) were used in the same combination as described above, again using each ink for inkjet recording, and discharge of ink from all the nozzles of the inkjet printer was confirmed. Then, the sheet was output to 100 sheets of recording paper, and the discharge stability was evaluated based on the following criteria.

The results are shown in tables 5 and 6 below.

A: almost no printing disorder from the start to the end of printing

B: output with occurrence of printing disorder

C: printing is always disturbed from the start to the end of printing

[ Table 5]

Color phase

Colour degree

Density of printing

Light resistance

Ozone resistance

Moisture resistance

Discharge stability

Example 1

A

B

A

Example 2

A

Example 3

A

Example 4

C

B

A

Example 5

C

B

A

Example 6

C

B

A

B

A

Example 7

A

Example 8

C

B

A

Example 9

A

Example 10

C

B

A

B

A

Example 11

A

Example 12

A

Example 13

A

Example 14

A

Example 15

A

Example 16

A

Example 17

A

Example 18

A

B

A

Example 19

A

Example 20

A

Example 21

A

B

A

Example 22

A

Example 23

A

B

A

Example 24

A

Example 25

A

Example 26

A

Example 27

A

[ Table 6]

Color phase

Colour degree

Density of printing

Light resistance

Ozone resistance

Moisture resistance

Discharge stability

Example 28

A

Example 29

A

Example 30

C

B

A

Example 31

C

B

A

Example 32

C

B

A

B

A

Example 33

C

B

A

Example 34

C

B

A

Example 35

A

Comparative example 1

C

B

C

A

Comparative example 2

C

B

C

A

Comparative example 3

A

C

B

A

Comparative example 4

A

C

B

A

Comparative example 5

C

B

A

Comparative example 6

A

C

B

A

Comparative example 7

A

C

A

Comparative example 8

A

C

B

C

A

Comparative example 9

C

D

C

B

Comparative example 10

A

B

C

A

Comparative example 11

A

B

C

A

Comparative example 12

A

C

B

A

Comparative example 13

A

C

B

A

Comparative example 14

C

B

A

Comparative example 15

C

B

A

Comparative example 16

C

B

A

Comparative example 17

A

C

A

Comparative example 18

A

C

A

Comparative example 19

C

B

Comparative example 20

C

B

C

B

As is clear from the results in tables 5 and 6, the inks of the examples using the compound of the present invention are excellent in hue, chroma, tinctorial strength (print density), light fastness, ozone fastness, moisture resistance and ejection stability.

Industrial applicability

The present invention has been described in detail and with reference to specific embodiments thereof, but it will be apparent to one skilled in the art that various changes or modifications can be made therein without departing from the spirit and scope thereof.

The present application is based on japanese patent application 2016 (japanese application 2016-.

Claims

1. A coloring composition, comprising:

a compound represented by the following general formula (1), and

at least one compound selected from the group consisting of a compound represented by the following general formula (D) and a compound represented by the following general formula (E),

general formula (1)

General formula (1)) In, R¹、R⁵、R⁶And R¹⁰Each independently represents an alkyl group having 1 to 6 carbon atoms, R⁴、R⁹、R¹²、R¹⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an ionic hydrophilic group selected from a carboxyl group, a sulfo group, a phosphono group and salts thereof, R¹¹、R¹³、R¹⁴、R¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Represents a hydrogen atom, R²、R³、R⁷And R⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a substituent represented by the following general formula (A), R²、R³、R⁷And R⁸At least 1 of them represents a substituent represented by the following general formula (A);

general formula (A)

In the general formula (a), X represents a substituent represented by the following general formula (X1), general formula (X2), or general formula (X3); represents a bonding bond to a benzene ring;

general formula (X1)

In the general formula (X1), R⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵Each independently represents a hydrogen atom or a substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group and salts thereof, wherein R is⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵Satisfies the following condition (i) or (ii); denotes a bond to a sulfur atom;

condition (i): r⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group;

condition (ii): r⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵At least 2 of which represent carboxyl groups;

general formula (X2)

In the general formula (X2), R⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷Each independently represents a hydrogen atom or a substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group and salts thereof, wherein R is⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The following condition (iii) or (iv) is satisfied; denotes a bond to a sulfur atom;

condition (iii): r⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group;

condition (iv): r⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷At least 2 of which represent carboxyl groups;

general formula (X3)

In the general formula (X3), R⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷Each independently represents a hydrogen atom or a substituent selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group and salts thereof, wherein R is⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷Satisfies the following condition (v) or (vi); denotes a bond to a sulfur atom;

condition (v): r⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷At least 1 of which represents a hydroxyl group and at least 1 represents a carboxyl group;

condition (vi): r⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷At least 2 of which represent carboxyl groups;

in the general formula (D), R₂₁And R₂₂Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

Y₂₁and Y₂₂Each independently represents a phenoxy group substituted or unsubstituted with a sulfo group, a carboxyl group or a salt thereof, or a naphthyloxy group substituted or unsubstituted with a sulfo group, a carboxyl group or a salt thereof;

xd represents 1, 2-diaminoethylene, 1, 4-diaminobutylene or 1, 6-diaminohexylene;

M⁴represents a hydrogen atom or a counter cation; m⁴May be the same or different;

in the general formula (E), R₃₁Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

Y₃₁represents a hydroxyl group or a salt thereof;

M⁵represents a hydrogen atom or a counter cation; m⁵May be the same or different;

X₃₁represents a group represented by the following general formula (E-1);

in the general formula (E-1), R₃₂、R₃₃、R₃₄、R₃₅And R₃₆Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or-COOM ', and M' represents a hydrogen atom or a counter cation; wherein R is₃₂、R₃₃、R₃₄、R₃₅And R₃₆At least 1 of them represents an alkyl group having 1 to 8 carbon atoms or-COOM'; denotes a bond to a carbon atom,

the total content of the compound represented by the general formula (1), the compound represented by the general formula (D) and the compound represented by the general formula (E) in the coloring composition is 2.0-5.0 mass%,

when the content of the compound represented by the general formula (1) is W₁W represents the content of the compound represented by the general formula (D)_DW represents the content of the compound represented by the general formula (E)_EWhen W is₁/(W_D+W_E) The mass ratio of (A) is 90/10-60/40.

2. The coloring composition according to claim 1,

x in the general formula (A) represents a substituent represented by the general formula (X1), and R in the general formula (X1)⁴⁰¹、R⁴⁰²、R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵The condition (i) is satisfied.

3. The coloring composition according to claim 1,

x in the general formula (A) represents a substituent represented by the general formula (X2), and R in the general formula (X2)⁵⁰¹、R⁵⁰²、R⁵⁰³、R⁵⁰⁴、R⁵⁰⁵、R⁵⁰⁶And R⁵⁰⁷The condition (iii) is satisfied.

4. The coloring composition according to claim 1,

x in the general formula (A) represents a substituent represented by the general formula (X3), and R in the general formula (X3)⁶⁰¹、R⁶⁰²、R⁶⁰³、R⁶⁰⁴、R⁶⁰⁵、R⁶⁰⁶And R⁶⁰⁷The condition (v) is satisfied.

5. The coloring composition according to claim 1 or 2, wherein the betaine compound is contained in the coloring composition in an amount of 0.01 to 10.0% by mass.

6. An ink for inkjet recording, which uses the coloring composition according to any one of claims 1 to 5.

7. An ink jet recording method using the ink for ink jet recording according to claim 6.

8. An ink cartridge for an ink-jet printer filled with the ink for ink-jet recording according to claim 6.